Classifications

• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
  • C05G5/00—Fertilisers characterised by their form
  • C05G5/30—Layered or coated, e.g. dust-preventing coatings
  • C05G5/38—Layered or coated, e.g. dust-preventing coatings layered or coated with wax or resins
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05C—NITROGENOUS FERTILISERS
  • C05C1/00—Ammonium nitrate fertilisers
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05C—NITROGENOUS FERTILISERS
  • C05C9/00—Fertilisers containing urea or urea compounds
  • C05C9/005—Post-treatment
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
  • C05D9/00—Other inorganic fertilisers
• • C—CHEMISTRY; METALLURGY
  • C05—FERTILISERS; MANUFACTURE THEREOF
  • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
  • C05G5/00—Fertilisers characterised by their form
  • C05G5/30—Layered or coated, e.g. dust-preventing coatings

Definitions

• the instant disclosure is directed towards fertilizer compositions including nitrogen containing compositions (e.g, urea) and release agent(s). More specifically, fertilizer compositions and methods of making the same are provided, where the fertilizer compositions include an inner portion, comprising a nitrogen containing material (e.g. volatilization prone nitrogen containing material like urea or leaching/run-off prone nitrogen containing material like ammonium nitrate, diammonium phosphate, or organic-based materials/manure) and an outer portion (e.g. coating or shell) including at least one release agent.
• the release agent is configured to promote a slow release/controlled release of the material in the inner portion
• the release agent is configured to provide: (a) soil conditioners such as increased soil buffering capacity; (b) soil amelioration such as increased soil moisture capacity; (c) minimization of runoff of nutrients such as nitrogen and phosphorous via ammonium binding and phosphate adsorption; (d) nutrients (e.g. micronutrients s macronutrients) to the soil; (e) a physical barrier to the volatilization and/or evaporation and/or leaching of the nitrogen-based material (e.g. urea) and/or inhibits the urease enzyme thereby slowing controlling the release of the material in the inner portion of the fertilizer; and combinations thereof.
• soil conditioners such as increased soil buffering capacity
• soil amelioration such as increased soil moisture capacity
• minimization of runoff of nutrients such as nitrogen and phosphorous via ammonium binding and phosphate adsorption
• nutrients e.g. micronutrients s macronutrients
• Nitrogen containing fertilizer e.g. urea
• fertilizer can be applied to soil in a solid s prilled form.
• the nitrogen containing fertilizer can be broken down to ammonia by proteins in the soil (urease).
• the resultant ammonia can volatilize (evaporate) under certain conditions before it is taken up by plants.
• ammonium nitrate is water soluble and susceptible to losses of nutrients arising from leaching or field run-off.
• the present disclosure relates to fertilizer compositions that include a nitrogen containing material (e.g. urea) and a release agent, where the release agent is configured to provide a controlled release and/or slow release fertilizer (e.g. reduce, prevent, or eliminate the volatilization or leaching/rim-off of the nitrogen containing material).
• a nitrogen containing material e.g. urea
• a release agent e.g. reduce, prevent, or eliminate the volatilization or leaching/rim-off of the nitrogen containing material.
• tlie release agent is believed to provide a physical barrier to protect the urea from being broken down (i.e. into urease). Also, without being bound by a particular mechanism or theory, the release agent (e,g. bauxite residue) is believed to remove dissolved ammonia, which can slow the release of nitrogen further. Without being bound by a particular mechanism or theory, the release agent is believed to provide structural integrity by preventing release agent removal (due to processing and/or handling) and or improving the malleability of the final product.
• fertilizer means: a substance used to make a growing medium (e.g. soil) more fertile.
• a fertilizer includes: a nitrogen containing material (e.g. urea, ammonium nitrate, diaramonium phosphate, manure, anhydrous ammonia, ammonium sulfate, ammonium phosphates, calcium nitrate,, or combinations thereof).
• the fertilizer includes an outer coating, layer, and/or shell having at least one release agent (e.g. release agent with optional binder, filler, and/or additive) over an inner portion of nitrogen containing material ⁇ e.g. a urea composition or material).
• the outer layer/portion comprises a coating (e.g. complete shell which encases the Inner portion).
• the outer layer/portion comprises at least one partial covering (e.g. in a multi-layered fertilizer composition), which promotes a slow release or controlled release of the inner portion, which is retained inside the multiple layers.
• the outer layer includes a plurality (e.g. two, three, four, or more) of partial layers, which cooperate to act as a single outer layer in promoting a slow release or controlled release of the inner portion, which is retained inside the multiple layers,
• the fertilizer form means: the shape or structure of something (as distinguished from its material composition).
• the fertilizer form includes: pellets, prills, granules, disks, particulate, powder, and combinations thereof,
• the pellets have at least one of: an outer layer, a coating, and/or shell
• the prills have at least one of: an outer layer, a coating, and/or shell.
• the granules have at least one of: an outer layer, a coating, and/or shell.
• the disks have at least one of: an outer layer, a coating, and/or shell.
• the particulates have at least one of: an outer layer, a coating, and/or shell
• the powder has at least one of: an outer layer, a coating, and/or shell.
• the fertilizer composition of the instant disclosure Is in a single form (i.e. pellets, prills, granules, disks, particulate, or powder). In some embodiments, the fertilizer composition of the instant disclosure is in multiple forms (i.e. a mixture of two or more forms, including pellets, prills, granules, disks, or powder).
• prill means: a pellet formed by generating droplets allowing the drops to solidify.
• the release agent(s) is/are added nitrogen containing material prior to prilling.
• the release agent(s) is/are added to nitrogen containing material after prilling (Le. co-prilling or coating after the nitrogen containing material product is prilled).
• the mesh size of a prill produet is between 4 and 20 mesh (i.e. -4700 microns - ⁇ 3G microns),
• pellet means a solid body (e.g. spherical, rounded, cylindrical).
• the nitrogen containing material and release agent(s) are ground (e.g. milled), mixed, and then pelletized together to form a pellet, which contains both nitrogen containing material and release agent(s) therein, at a desired weight percentage.
• the mesh size of a pelletized product is between 4 and 20 mesh,
• powder means: matter in a finely divided state.
• the nitrogen-containing material and release agent(s) are ground (either independently or in combination) to yield a powder product having a particular average particle size.
• the mesh size of a powder produet is greater than 20 mesh.
• the nitrogen containing material is crushed (i.e. reduced in size from prilled or pellet form) into smaller pieces (which are particulate in form as opposed to powder).
• the niirogen containing material is combined with the release agent(s) during the production process to form a composition having both nitrogen containing material and release agent(s) therein.
• the mesh size of a granule product is between 4 and 20 mesh.
• the fertilizer composition comprises a homogenous mixture.
• the fertilizer composition comprises a heterogeneous mixture
• the fertilizer compositions include: uncoated materials, coated materials, and or multi-coated materials (i.e. more than one coating).
• outer means: situated outside or external
• coating means: a layer of something which covers something else
• shell means: an outer casing. In some embodiments, the shell protects the inner portion (e.g, by enclosing/encasing it),
• encasing means: surrounding on all sides.
• partial means: existing only in part, in some embodiments, the coating is a partial coating, in that it does not completely surround the inner core on all sides. As one example, a partial coating covers one side (or end) of the inner core. As another example, a partial coating substantially surrounds the inner core but has discontinuous regions (e.g. small holes or ridges where mere is no coverage),
• multiple partial coatings are configured to cooperate as an encasing layer (e.g. multiple layers of 50% coverage cooperate in the same way that a single encasing layer would, to prevent the inner core from volatilization evaporation).
• nitrogen containing material means: a substance having nitrogen in its composition or make-up
• a nitrogen containing material is a fertilizer having nitrogen therein (e.g. m the form of urea, ammonia, or ammonium).
• nitrogen containing material include: urea composition, urea, ammonium nitrate, diarnmonium phosphate, nitrogen-based fertilizers (with fertiliser and optional fillers and/or inert agents), organic based materials like manure, and combinations thereof.
• urea composition means: a material having urea
• urea composition means urea and unavoidable impurities (e.g. Included as part of the manufacture process).
• urea composition refers to a urea fertilizer (e.g. Including urea with optional fillers and/or inert agents),
• 4i urea means: CG(M3 ⁇ 4) 2 ,
• release agent means: a material or component that impacts (e.g. reduces, restricts, prevents, and/or eliminates) the ability of another material to escape from confinement and/or be released.
• a release agent is used in combination with a filler, binder, and/or additive (as set out below).
• the release agent acts as a binder, filler, and or additive in the fertilizer composition,
• release agents include bauxite residue, layered double hydroxides (e.g. hydrotalcite, hydrocaiumite), apatite, electrostatic precipitator fines, bauxite, red lime, neutralized bauxite residue, da sonUe, fukalite, aluminum hydroxide, smelter grade alumina (SGA), and combinations thereof.
• bauxite residue layered double hydroxides (e.g. hydrotalcite, hydrocaiumite), apatite, electrostatic precipitator fines, bauxite, red lime, neutralized bauxite residue, da sonUe, fukalite, aluminum hydroxide, smelter grade alumina (SGA), and combinations thereof.
• binder means: a material that is used to hold things together. In some embodiments, the binder is used to fill in the cracks on the outer portion or coating.
• binders include: commercially available pellet binders (e.g. used in the chemical or pharmaceutical industries), polymers, inorganic solvents (e.g. water), organic solvents, alginates, alginate-calcium chloride solutionis), lignosulfonates, aftapulgite, asphalt wax, resin, reactive metal salts with reactive metal oxides or hydroxides, molasses, Portland cement, silicates (e,g. sodium silicates), or naturally occurring clay (e.g. bentoniie clay), starch, eora starch, sugar, sugar water, flour, guar gum, plaster of Paris, waste from paper mills, cellulose derivatives, and combinations thereof.
• filler means: a material used to fill a cavity or increase bulk.
• filler include: wax (e.g. paraffin wax, agricultural waxes), polymers, silicates, or Portland cement, and combinations thereof,
• fertilizer additive means; a materia] added to fertilizer (e.g. in order to impart a characteristic or property), In some embodiments, the fertilizer additive is selected in order to add a particular nutrient or several nutrients to the soil (e.g. where the soil is deficient in these nutrients).
• a non-limiting example of a fertilizer additive includes gypsum, which, when present in one or more of the fertilizer compositions of the instant disclosure, provides sulfur to the growing medium (e.g. soil).
• byproduct of metal production means: a compound or class of materials that is produced by one or more processes of making non-ferrous metal (e.g. aluminum). Some non-limiting processes include: the Bayer process, smelting, refining, easting, recycling, producing various products, product forms, and combinations thereof,
• release agents that are products of aluminum production and/or processing include: apatite, electrostatic precipitator fines (ESP), Bayer process byproducts, and combinations thereof.
• ESP electrostatic precipitator fines
• Bayer process byproducts and combinations thereof.
• Bayer process byproduct means: a substance produced during the reduction of bauxite to form produce alumina.
• release agents that are Bayer process byproducts include; layered double hydroxides, hydrota!cite, hydrocalumite, bauxite residue, neutralized bauxite residue, dawsonlte, ilikaiite, aluminum hydroxide, smelter grade alumina (SGA), and combinations thereof.
• layered double hydroxide means: a class of compounds which are characterized by multiple (e.g. two) positively charged layers and weakly bound, often exchangeable central ion(s) (e.g. negatively charged ions) located in the interlayer (middle) region.
• LDHs are commonly referred to by the following generic chemical formula:
• ⁇ - imiiing examples of LDH compounds include: hydrotalcites, hydrocaiumste, hydromagnesite, takovite, woolite, and combinations thereof.
• "unavoidable minor components 5 ' means: various chemicals and minerals that are present in the release agents.
• Some non-limiting examples include: iron-containing compounds (e.g, Fe 2 ⁇ 3 ⁇ 4; FeOOH; silicon-containing compounds (e.g, SIOj): titanium-containing compounds (e.g. T1O2); sodium -containing compounds (e.g. aOH; NaNi3 ⁇ 4; Na 3 P04; Na 2 HP0 4 ; N aCC ); calcium-containing compounds (e.g. CaO; C (GH)2; CaSG ⁇ CaCOs; €&3( ⁇ 1( ⁇ ⁇ ) ⁇ ; TCA (tricalcium a!uminate)); magnesium- containing compounds (e.g.
• gO gO
• Mg(OH)2 MgCOa
• anionic organic compounds e.g, oxalate (sodium oxalate), formate (ammonia formate), acetate,
• aluminum-containing compounds e.g. Al(OH)3; AIOOH; and combinations thereof.
• the total weight percent of unavoidable minor components is not greater than 30 t % (i.e. for each compound).
• the unavoidable minor component is: not greater than 30 wt %; not greater than 25 wt %; not greater than 20 wt %; not greater than 15 wt, %; not greater than 10 wt. %; not greater than 7 wt. %; not greater than 5 wt %; not greater than 3 wt, 3 ⁇ 4; not greater than 1%; not grealer than 0.5 wt. %; not greater than about 0 J wt. %; or not greater than 0.1 wt. %,
• the unavoidable minor component is; not less than 30 wt. %; not less than 25 wt. %; not less than 20 wt. %; not less than 15 wt. %; not less than 10 wt. %; not less than 7 wt. 3 ⁇ 4; not less than 5 wt, %; not less than 3 wt. %; not less than 1%; not less than 0.5 wt. %; or not less than about 0,1 wt. .
• the unavoidable minor component content is not greater than 30 wt, % for each component.
• the content of unavoidable minor components is not greater than 30 wt, % for each component.
• the content of unavoidable minor components is not greater than 20 wt % for each component
• the content of unavoidable minor components is not greater than 20 wt, % for each component.
• the content of unavoidable minor components is not greater than about 1 wt. %.
• intercalated means: a substances which has another substance or material inserted between or among existing elements or layers.
• an LDH is Intercalated with its eentral/interlayer region being replaced with other anions or compounds.
• Non-limiting examples of intercalated LDH include: herbicides, pesticides, anti-fiiBgal agents, supplemental nutrients (e.g. phosphorous compounds, nitrogen compounds, sul&r compounds, trace-element compounds, and combinations thereof).
• the LDH is Intercalated with a nitrate.
• the LDH is intercalated with a sulfate.
• the LDH is intercalated with a phosphate.
• LDH comprises hydrotakite (HTC). In some embodiments, LDH comprises hydrocalnmite,
• hydrotaleite means: a layered double hydroxide of the following formula:
• Non-limiting examples of groups of materials within the hydrotalcites supergroup include: hydrotalcites group, quintinite group, fougerite group, woodwardite group, glaucerinite group, cuafstibite group, hydrocaiumite group, and unclassified.
• Non-limiting examples of hydrotalcites include: pyroaurite, stichtite, meixnerite, iowaite, droninoite, woodailite, desaureisite, takovite, reevesite, jamborile, qmotinste, channarite, earesite, zaccagnaite, chrlomagaluminite, fougerite, woodwardite, zincowoodwardite ⁇ hotiessite, elaucocerinite, hydrowoodwardiie, carrboydite, hydrohonessite, mountkeithlte, sincaluminite, wasmlandiie, shigaite, rnkischerite, motukoreaite, natroglaucocerinite, karchevskylte, euaistibite, xincalstibite, hydroelumite, kuzeHte, coa!ingite, brugnaielli
• Non-limiting examples of intercalated hydrotalcites ⁇ sometimes called iHTC) include; HTC -carbonate, HTC -phosphate, HTC-nitrate, and combinations thereof.
• apatite means: a phosphate mineral having calcium phosphate with some fluorine, chlorine, and other elements. In some embodiments, apatite is neutralized with group of phosphate minerals.
• an apatite compound is hydroxyapatite
• bauxite residue means: particulate alkaline clay produced as a byproduct of the Bayer Process (e.g, the process of refining of bauxite ore into alumina).
• bauxite residue (sometimes called red mud) includes a plurality of metals, metal oxides, clay, and zeolites.
• the bauxite residue is generally free from draining liquids and is neutralized from its original form (i.e. s!nrry having volatile components at a pH of approximately 13).
• the bauxite residue comprises a pH of 7, In some embodiments, the bauxite residue comprises a pH of 8. In some embodiments, the bauxite residue comprises a pH of 9. In some embodiments, the bauxite residue comprises a pH of 10. In some embodiments, the bauxite residue comprises a pH of 1 1. In some embodiments, the bauxite residue comprises a pH of 12, In some embodiments, the bauxite residue comprises a pH of between about 7 and 9.
• bauxite residue may be neutralized via acid or neutralized by the atmosphere (e.g. via reaction with ambient carbon dioxide and/or contact with anthropogenic carbon dioxide).
• acid neutralized means: a material (e.g. bauxite residue) which is made chemically neutral (or closer to neutral) through the addition of an acid.
• Non-limiting acids include; phosphoric acid, nitric acid, sulfuric acid, organic acids, minerals, and combinations thereof.
• the bauxite residue is neutralized with aluminum hydroxide, forming bauxire residue ⁇ NO 3 ).
• the resulting bauxite residue compound has a nitrate content of 5- 10 w 3 ⁇ 4,
• the bauxite residue is neutralized with phosphoric acid, forming bauxite residue ⁇ PO4).
• the resulting bauxite residue compound has a phosphate content of 5 -10 wt. %,
• phosphogypsum Is used to neutralize bauxite residue are used to neutralize bauxite residue.
• dawsonite means: a sodium aluminate carbonate hydroxide compound, In some embodiments, dawsonite is a byproduct of the refining step(s) (e.g. after addition of sodium hydroxide in the Bayer Process),
• fukalite means: a calcium silicate carbonate compound.
• fukalite is a hydroxide or a fluoride derivative of a calcium silicate carbonate compound.
• fukalite is a byproduct of the refining stepfs) (e.g. after addition of sodium hydroxide in the Bayer Process).
• dawsonite, fukalite, hydroxyapatite, and hydroxymagnesite are components in bauxite residue. In some embodiments, dawsonite, fukahte, hydroxyapatite, and hydroxymagnesite are components in bauxite.
• ESP means the dust that comes from an electrostatic precipitator (i.e. used to clean industrial process exhaust streams).
• ESP comprises (e.g. as a major component) alumina fines which are removed from exhaust fumes of industrial processes,
• bauxite means: an ore from which alumina is extracted.
• bauxite ore comprises: alumina, iron oxides, silicates, calcium carbonate, sodium hydroxide, calcium oxide, titama, manganese oxide, magnesium oxide, phosphates.
• bauxite comprises at least 3Gwt. % alumina; at least 40% alumina; at least 50% alumina; at least 60% alumina; at least 70 wt, %; at least 80 wt. %; at least 90 wt, %, or higher.
• hydromagnesite means: a magnesium carbonate mineral.
• dolomite means an ore having magnesium carbonate and calcium carbonate therein.
• red lime means; a mixture of iriealeium aluminate (TCA) and calcium carbonate, with some iron oxides present, which is a byproduct of aluminum processing.
• TCA is the major component (i.e. at least 51 wt. %) in red lime.
• TCA is: at least 50 wt. %: at least 55 wi. %; at least 60 wt. %; at least 65 wt. %; at least 70 wt, %; at least 75 wt. %; at least wt. 80%; at least 85 wt. %; at least 90 wt %; at least 95 wi, %; or at least 99 wt. % (with the remainder being calcium carbonate and/or iron oxides).
• TCA is the major component (i.e. not greater than 51 wt. %). In some embodiments, TCA is: not greater than 50 wt, %: not greater than 55 wt. %; not greater than 60 wi, %; not greater than 65 wt. %; not greater than 70 wt. %; not greater than 75 wt. %; not greater than, 80 wt %; not greater than ⁇ 5 wt, %; not greater than 90 wt. %; not greater than 95 wt. 3 ⁇ 4; or not greater than 99 wt. % (with the remainder being calcium carbonate and/or iron oxides),
• the fertilizer composition includes a pH adjusting component.
• pH adjusting components include: nitric acid, phosphoric acid, bauxite residue, and combinations thereof,
• the pH adjusting component is Intercalated into the release agent (e.g, LDH),
• the pH adjusting component is blended to/mixed with the release agent (e.g. neutralized bauxite residue).
• the fertilizer composition includes a plant nutrient.
• plant nutrients include; N, P, K f Mg, Ca, K, trace elements (Fe s n, metals present In the release agents), and combinations thereof,
• slow release fertilizer means: a fertilizer having a gradual release of nutrients available for plant uptake (e.g, where ti*e release rate cannot be predicted within prescribed time limits— or can be estimated only very roughly ⁇ .
• a slow release fertilizer e.g, release agent coated urea fertilizer composition
• a referenced fertilizer e.g, irrea fertilizer composition
• s a slow release fertilizer reduces volatilization of urea as compared to the reference fertilizer
• Non-limiting examples of slow-release products are coated or partially coated fertilizers, In which the release of soluble nutrients is controlled through the coating, which includes soluble nutrient compounds, water insoluble, or slowly available water-soluble components.
• a slow release fertilizer is a controlled release fertilizer, [0075]
• controlled release fertilizer means: a fertilizer having a gradual release of nutrients available for plant uptake, where the release rate is predictable within certain limits.
• controlled release fertilizer products release plant nutrients in a form available for plant uptake at a slower rate (and at a quantifsably reduced rate) titan that of unmodified fertilizer product (I.e, where s in some embodiments, the controlled release fertilizer has insoluble portions and/or low solubility portions and the fertilizer is soluble).
• the Tennessee Valley Authority immersion test s used to evaluate a controlled release characteristic of a fertilizer composition. This test calls for adding 50 g of sample (fertilizer composition) to 250 mL of water, followed by heating the mixture at 100° F for a specified period of time in order to quantify the release rate of the fertilizer sample (based on the nitrogen containing material release rate).
• fertilizer compositions of the instant disclosure comprise a release rate of not greater than 20 wt % of nitrogen containing material In a 24 hour period (e.g. when measured in accordance with the TV A test). In some embodiments, the fertilizer compositions of the instant disclosure comprise a release rate of not greater than 50 wt. % of the nitrogen containing material in a 7 day period (when measured in accordance with the TVA test). In some embodiments, the fertilizer compositions of the instant disclosure comprise a release rate of not less than SO wt. % of the nitrogen containing material in a 30 day period (when measured in accordance with the TVA test).
• enhanced efficiency fertilizer means: a fertilizer product with characteristics that allow increased nutrient availability and reduce the potential of nutrient losses to the environment (e,g. gaseous losses via evaporation, leaching of nutrients, or runoff of nutrients via water runoff), as compared to an appropriate reference (non-modified, uncoated fertilizer),
• one or more of the fertilizer compositions include at least one of the following characteristics: growing medium enhancement, increased growing medium moisture content, increased growing medium buffering capacity, decreased phosphorous runoff from the growing medium, added rnicronutrients to the growing medium, decreased urease activity, inhibited urease activity, decreased ammonia absorption., ammonium binding, and combinations thereof.
• evaporation means: a tendency of a material to pass off in a vapor
• the fertilizer composition has an average ize of: at least 1/8"; at least 1/4"; at least 3/8"; at least 1/2"; at least 5/8"; at least 3/4"; or at least 1 ", In some embodiments, the fertilizer composition has an average size of: not greater than 1/8"; not greater than 1/4"; not greater than 3/8"; not greater than 1/2"; not greater than 5/8"; not greater than 3/4"; or not greater than 1".
• the outer portion (e,g, whether a layer, multi-layer, a coating, and/ or a shell) has an average thickness of: at least 25 microns, at least 50 microns; at least 75 microns; at least 100 microns; at least 125 microns, at least 150 microns; at least 175 microns; at least 200 microns; at least 225 microns, at least 250 microns; at least 275 microns; at least 300 microns; at least 325 microns, at least 350 microns; at least 375 microns; at least 400 microns; at least 425 microns, at least 450 microns at least 475 microns; at least 500 microns; at least 525 microns, at least 550 microns; at least 575 microns; at least 600 microns; at least 625 microns, at least 650 microns; at least 675 microns; at least 700 microns; at
• the outer portion (e.g. whether a layer, multi-layer, a coating, and/ or a shell) has an average thickness of; not greater than 25 microns, not greater than 50 microns; not greater than 75 microns; not greater than 100 microns; not greater than 125 microns, not greater than 150 microns; not greater than 175 microns; not greater than 200 microns; not greater than 225 microns, not greater than 250 microns; not greater than 275 microns; not greater than 300 microns; not greater than 325 microns, not greater than 350 microns; not greater than 375 microns; not greater than 400 microns; not greater than 425 microns, not greater than 450 microns; not greater than 475 microns; not greater than 500 mierons; not greater than 525 microns, not greater than 550 microns; not greater than 575 rnierons; not greater than 600 microns; not greater than 625 microns
• the onter portion is; from 50 microns to 250 microns, In some embodiments, the onter portion is: from about 100 to about 200 microns.
• a fertilizer composition comprising; an inner portion comprising a nitrogen containing compound; and an outer portion coating the inner portion, the outer portion configured with a release agent comprising a layered double hydroxide, wherein the onter portion comprises not greater than 30 wt % of the fertilizer composition.
• the nitrogen containing compound is urea.
• die layered double hydroxide is selected form the group consisting of: hydrotalclte, hydrocalumite, and combinations thereof.
• the outer portion farther comprises at least one of: a binder, a filler, and an additive.
• the outer layer comprises hydrotalcite and wax.
• a fertilizer composition comprising: an inner portion comprising urea; and an outer portion coating the inner portion, the outer portion configured with a release agent comprising a hydrotalcite, wherein the outer portion comprises not greater than 20 wt % of the fertilizer composition,
• the outer portion further comprises a binder.
• the binder further comprises a wax in an amount not exceeding 5 wt. % of the fertilizer composition.
• a fertilizer composition comprising: an inner portion comprising urea; and an outer portion encasing the inner portion, the outer portion configured with a release agent including a Bayer Process byproduct selected from the group consisting of: bauxite residue and layered double hydroxides.
• the outer portion comprises 5 wt. % to 30 wt. % of the total weight of the composition.
• the outer portion comprises 10 wt. % to 20 wt, % of the total weight of the composition.
• the release agent is bauxite residue. In some embodiments, the release agent is hydrotalcite.
• the release agent is configured to slow the release of urea into a growing medium.
• a fertilizer composition comprising: an inner portion comprising: a nitrogen containing material; and an outer portion encasing (e.g. completely surrounding) the inner portion, the outer portion comprising a release agent.
• a fertilizer composition comprising: an inner portion comprising a urea composition; and an outer portion encasing (e.g. completely surrounding) the inner portion, the outer portion comprising a release agent.
• a fertilizer composition comprising: an inner portion comprising a nitrogen containing material; and an outer portion encasing (e.g. completely surrounding) tlie inner portion, the outer portion comprising a release agent; wherein the outer portion comprises at least 5 wi. % to not greater than 30 vvt. % of the total weight of the composition.
• a fertilizer composition comprising: an inner portion comprising a nitrogen containing material and bauxite residue; and an outer portion encasing (e.g. completely surrounding) the Inner portion, the outer portion comprising a release agent,
• a fertiliser composition comprising: an inner portion comprising; a nitrogen containing material; and an outer shell around the inner portion, the outer shell comprising a release agent.
• a fertilizer composition comprising: an inner portion comprising a nitrogen containing material; and an outer shell around the inner portion, the outer shell comprising a release agent and at least one of: a filler, a binder, and an additive,
• a fertilizer composition comprising: an inner portion comprising: a nitrogen containing material and a release agent; and an outer portion comprising a release agent, where the outer portion is configured to completely surround the inner portion.
• a fertilizer composition comprising: an inner portion comprising; a nitrogen containing composition and a coating comprising a release agent, where the coating (sometimes the outer portion) is configured to cover 30% to 100% of the inner portion (e,g, outer portion is a partial coating/porous coating).
• a fertilizer composition comprising: an inner portion comprising: a nitrogen containing material and bauxite residue; and coating comprising a release agent, where the coating ⁇ sometimes the outer portion) is configured to cover 30% to 100% of the inner portion (e.g. outer portion is a partial coating/porous coating).
• the coating covers: at least 30 % of the surface of the inner core; at least 40 % of the surface of the irmer core; at least 50 % of surface of the inner core; at least 60 % of surface of the inner core; at least 70% of the surface of the inner core; at least 80% of the surface of the inner core; at least 90% of the surface of the Inner core; at least 95% of the surface of the inner core; or at least 99% of the surface of the inner core.
• the coating covers: not greater than 30 % of the surface of the inner core; not greater than 40 % of the surface of the inner core; not greater than 50 % of surface of the irmer core; not greater tlian 60 % of surface of the irmer core; not greater than 70% of the surface of the inner core; not greater than 80% of the surface of the inner core; not greater than 90% of the surface of the inner core; not greater than 95% of the surface of the inner core; or not greater than 99% of the surface of the irmer core.
• the outer portion covers 100% of the inner portion.
• a fertilizer composition comprising; a plurality of layers comprising a nitrogen containing material (e.g. urea) interspaced with a plurality of layers comprisirsg release agent, wherein outermost layer of the composition comprises a release agent coating/shell (e.g, including wax and/or polymer).
• the nitrogen based material differs between layers (e.g. of the multi-layers, each individual nitrogen containing material layer is selected from this group: urea, ammonium nitrate, manure, diammonlum phosphate, and combinations thereof.)
• a fertiliser composition comprising: a plurality of layers comprising a nitrogen material (e.g. urea, ammonium nitrate, diammonium phosphate, manure, and combinations thereof) interspaced with a plurality of layers selected from the group consisting of: a release agent, binder, filler, additive, and combinations thereof, wherein at least one layer comprises a release agent.
• the outer portion further comprises additives (e.g. binder, filler, additive).
• the fertilizer composition includes: uncoated nitrogen containing material (e.g. nitrogen fertilizer or manure in prilled, pelletized, or granular form) and coated fertilizer (e.g. an irmer core including a nitrogen containing material and an outer portion including a release agent.
• uncoated nitrogen containing material e.g. nitrogen fertilizer or manure in prilled, pelletized, or granular form
• coated fertilizer e.g. an irmer core including a nitrogen containing material and an outer portion including a release agent.
• the fertiliser comprises a blend of coated fertilizer having coatings of different thicknesses.
• the fertilizer comprises a blend of coated fertilizers, where at least some of the fertilizer comprises a single coating (e.g. partial and/or encasing) and at least some is mutli-layered.
• the fertilizer includes a blend of at least two average particle sizes (e.g. large and small sized fertilizers, with coated and uncoated variations).
• the outer portion (e.g. coating or layer) comprises: at least 5 wt %; at least 10 wt. %; at least I S wt. %; at least 20 wt. %; at least 25 wt. %; or at least 30 wt % of the total weight of the composition.
• the outer portion (e.g. coating or layer) comprises: not greater than 5 wt %; not greater than 10 wt ; not greater than 15 t %; not greater than 20 wt. %; not greater than 25 wt. %; or not greater than 30 wt. % of the iota! weight of the composition.
• At least one coating of the coated fertilizer composition inclndeSj in combination with a release agent was (e.g. paraffin), sugar polymer (e.g. alginate, alginate in a calcium chloride-water solution, sodium alginate, cellulose in alginate, alginfe acid), sugar polymer and wax, carboxyi c acid (also called a carboxylase, depending on the pH) (e.g. fatty acid, black liquor); po!yelectrolytes; polymers; Portland cement; and combinations thereof.
• a release agent was (e.g. paraffin), sugar polymer (e.g. alginate, alginate in a calcium chloride-water solution, sodium alginate, cellulose in alginate, alginfe acid), sugar polymer and wax, carboxyi c acid (also called a carboxylase, depending on the pH) (e.g. fatty acid, black liquor); po!yelectrolytes; polymers; Portland cement; and combinations thereof.
• alginate refers to a poiysaeharide derived from brown algae.
• alginate molecules are capable of crosslinking with one another (e.g. in the presence of calcium chloride and water), thus forming a viscous liquid (e.g. resembling gelatin).
• crosslinked alginate is configured to improve structural properties of the outer layer (e.g. coating).
• alginate and or crosslinked alginate is used in combination with at least one of a bayer byproduct, bauxite residue, LDH, hydrotalcite, and/or hydrocaiumiie,
• sodium alginate in order to form the cross-linked material, sodium alginate is sprayed with a calcium chloride solution (1 M or 3M) in place of water.
• At least one coating includes a release agent, and at least one other coating Includes at least one of a release agent, binder, filler, additive, wax, sugar polymer, carboxyiic acid, polyeieetrolytes, polymers, Portland cement, and combinations thereof,
• a method comprising: (a) forming a mixture (e,g, in a drum roller) of particulate a release agent and a nitrogen containing material; (b) spraying a liquid (e.g. water, industrial solvent) into the mixture to promote coating of the nitrogen containing material with the release agent (e.g. in some embodiments, liquid includes binder, additive, and/or filler); and (c) forming a coated composition, the fertilizer having: an inner portion of the nitrogen containing material and an outer portion (e.g. shell or coating) of the release agent (e.g. and/or filler, b nder, additive),
• a liquid e.g. water, industrial solvent
• the fertilizer having: an inner portion of the nitrogen containing material and an outer portion (e.g. shell or coating) of the release agent (e.g. and/or filler, b nder, additive),
• the method comprises: (d) baking the coated composition to remove the liquid and result in a fertilizer composition, in some embodiments, the method Includes curing the coating (e.g. through application of heat, light, and/or time).
• the coating includes silicate(s) ? the coating is baked, In one embodiment, when the coating includes Portland cement, it is allowed to cure at room temperature. In one embodiment, when the coating includes wax (e.g. and antt-caking agents), the coating solidifies at room temperature.
• the method comprises: (e) forming a mixture of coated composition and a release agent.
• the method comprises: repeating steps (b) through (c) on the mixture of coated composition and a release agent.
• the fertilizer composition comprises: a nitrogen containing compound (e.g. urea) admixed with an intercalated layered double hydroxide.
• a nitrogen containing compound e.g. urea
• the layered double hydroxide is intercalated with urea.
• the fertilizer composition comprise: a blended nitrogen containing compound (e.g. urea) with a release agent, which is coated in a release agent.
• a release agent e.g. urea
• the release agent is/are the same in the coating as it is in the blended core component.
• the release agent Is/are different in the coating as compared to the blended core component,
• the fertilizer composition includes: a nitrogen-containing compound (e.g. urea) blended with a release agent (e.g. including intercalated layered double hydroxide), which is coated with at least one release agent (where the release agent in the blend and coating may be the same or different release agents or combinations of release agents).
• a nitrogen-containing compound e.g. urea
• a release agent e.g. including intercalated layered double hydroxide
• fertiliser compositions of the instant disclosure are made by spraying the concentrated nitrogen-containing material solution (i.e. 96-99+ %) while simultaneously spraying a concentrated solution of the release agent(s) (e.g. suspended or in solution in a solvent) and eo-prilling the resulting fertilizer composition.
• the concentrated nitrogen-containing material solution i.e. 96-99+ %
• a concentrated solution of the release agent(s) e.g. suspended or in solution in a solvent
• fertilizer compositions of the instant disclosure are made by adding the release agent(s) to the concentrated nitrogen-containing material solution prior to prilling.
• fertilizer compositions of the instant disclosure are made by coating the release agent(s) onto the prill after the nitrogen-containing material prill is formed.
• a drum roller is used (e.g, with optional solvents and/or binders) to adhere and/or coat the release agent(s) onto the nitrogen-containing material prill
• the release agent(s) are mixed into the nitrogen-containing material solution (with optional solvents) and the resulting fertilizer composition is reerysia!lized from solution or suspension,
• nitrogen-containing material prills are ground with release agent(s) in a milling press and utilized in a powder form.
• the powder is mixed with binder(s) and rolled into agglomerated forms,
• the blended powder is mixed with a binder arid formed (e.g. pressed) into pellets or plates (e.g. with a disk- press or peptization process).
• the solution (or suspension) of nitrogen-containing material with release agents are spray dried.
• the solution (or suspension) of nitrogen-containing material with release agent(s) are agglomerated (e.g. pan agglomeration), followed by a peptization process,
• the bauxite residue is raw bauxite residue (e.g. utilized without an aeid neutralization step, in its in situ particle size distribution (without sieving)).
• the release agent, binder, filler, and or additive is added via vapor deposition (e.g. place urea on a screen above heated release agent, binder, filler, and/or additive (and/or solvent, liquid) such that the vapors (containing release agent, binder, additive, and/or filler) contact the surface of the urea to form an outer portion coating sheil on the urea (inner portion/core),
• vapor deposition e.g. place urea on a screen above heated release agent, binder, filler, and/or additive (and/or solvent, liquid) such that the vapors (containing release agent, binder, additive, and/or filler) contact the surface of the urea to form an outer portion coating sheil on the urea (inner portion/core)
• the release agent, binder, filler, and or additive was applied via dipping (e.g. placing the urea on a screen and dipping the screen and urea into a liquid containing release agent, binder, filler, and/or additive (with an optional solvent and/or liquid to suspend the release agent, binder, filler, and/or additive),
• binder,, filler, and/or additive is added to the release agent during the (e.g, simultaneous to) the release agent coaling onto the urea product.
• Figures IA-ID depict various embodiments of fertilizer compositions of the instant disclosure, each having an inner portion of a nitrogen containing material and an outer portion of a release agent.
• Figure 1A provides an inner portion including a nitrogen containing material (e.g. urea composition) and an outer portion comprising a release agent (e.g. in the form of a coating or shell).
• a nitrogen containing material e.g. urea composition
• a release agent e.g. in the form of a coating or shell
• Figure IB provides an inner portion including a nitrogen containing material (e.g. urea composition) and an outer portion comprising a release agent (e.g, in the form of a coating or shell), where the outer portion is thicker (e.g. a higher wt %) than that depicted in Figure 1 A.
• a nitrogen containing material e.g. urea composition
• a release agent e.g. in the form of a coating or shell
• Figure 1C depicts an inner portion including a nitrogen containing material (e,g, urea composition) and an outer portion (e.g. in the form of a coating or shell), where the two layers are partial layers (e.g. not a complete shell or coating, but rather, a porous or discontinuous layer).
• the first layer is includes a release agent, while the second layer includes a binder, additive, and/or filler.
• Figure ID provides an inner portion including a nitrogen containing material (e.g. urea composition) and an outer portion comprising a release agent (e.g. in the form of a coating or shell), where the outer portion has varying degrees of thickness (e.g. thicker vs. thinner areas) than that depicted in Figure 1 A.
• Figures 2A-2D depict various embodiments of fertilizer compositions of the instant disclosure, in which the inner portion includes: a nitrogen containing material (eg. urea composition) and a release agent and an outer portion comprises a release agent (e.g. in the form of a coating or shell).
• Figures 2A through 2D are similar to Figures 1 A through ID, but for the Inner portion includes a release agent in addition to the nitrogen containing material.
• Figures 3A-3D depict various embodiments of fertilizer compositions of the instant disclosure in which the composition includes multiple layers (e.g. a plurality of nitrogen containing material layers interspaced with a plurality of release agent layers).
• Figure 3A depicts an embodiment of a fertilizer composition having a plurality of coatings/layers.
• Figure 3B depicts an embodiment of a fertilizer composition having a combination of thin/thick layers, where one layer (e.g. the thick layer) is discontinuous (e.g. porous, partial covering).
• one layer e.g. the thick layer
• discontinuous e.g. porous, partial covering
• Figure 3C depicts an embodiment of a fertilizer composition having multiple partial layers.
• Figure 3D depicts an embodiment of a fertilizer composition having multiple layers, where each layer has varying thicknesses (thick and thin portions),
• Figure 4 depicts an embodiment of a fertilizer composition having an inner core (e.g. urea) and an outer shell, where the outer shell includes both a release agent and a binder, with the binder positioned over the top of the release agent.
• an inner core e.g. urea
• an outer shell includes both a release agent and a binder, with the binder positioned over the top of the release agent.
• Figure 5 is a chart of experimental data, the effect of wax type on nitrogen release rate (for HTC coated Urea).
• Figure 6 depicts a chart of experimental data, the effect of wax type on nitrogen release (for BR coated Urea).
• Figure 7 is a chart of experimental data, the effect of bauxite residue particle size on nitrogen release rate (for bauxite residue coated urea).
• Figure 8 is a chart of experimental data, illustrating the six week growth progress for lab scale growth studies trtil ng various types of control fertilizers and coated fertilizer
• Release agent coating additive 22 e.g. filler, binder, additive
• Figures 1A-1 D depict various embodiments of fertilizer compositions 10 (coated fertilizers) of the instant disclosure, each having an inner portion 12 of a nitrogen containing material 20 and an outer portion 14 of a release agent 24.
• Figure 1A provides a fertilizer composition having an inner portion 12 including a nitrogen containing material 20 (e.g. urea composition) and an outer portion 14 comprising a release agent 24 (e.g. in the form of a coating 16 or shell).
• Figure I B provides a coated fertilizer composition 10 having an inner portion 12 including a nitrogen containing material 20 (e.g. urea composition) and an outer portion 14 comprising a release agent 24 (e.g. in the form of a coating or shell), where the outer portion 14 is thicker (e.g.
• Figure 1C depicts a fertilizer composition having an inner portion 12 including a nitrogen containing material 20 (e.g. urea composition) and an outer portion 14 (e.g. in the form of a coating or shell), where the two layers are partial layers (e.g. not a complete shell or coating, but rather, a porous or discontinuous layer).
• the first layer is includes a release agent 24, while the second layer includes a binder 28, additive 30, and/or filler 26.
• Figure ID provides a fertilizer composition 10 having an inner portion 12 including a nitrogen containing material 20 (e.g.
• urea composition and an outer portion 14 comprising a release agent 24 (e.g, in the form of a coating or shell), where the outer portion 14 has varying degrees of thickness (e.g. thicker vs. thinner areas) than that depicted in Figure 1 A.
• a release agent 24 e.g. in the form of a coating or shell
• Figures 2A-2D depict various embodiments of fertiliser compositions 10 of the instant disclosure, in which the inner portion 12 includes: a nitrogen containing material 20 (e.g. urea composition) and a release agent 24 and an outer portion 14 comprises a release agent 24 (e.g, in the form of a coating or shell).
• Figures 2A through 2D are similar to Figures 1 A through ID, but for the inner portion 12 includes a release agent 24 in addition to the nitrogen containing material 20.
• Figures 3A-3D depict various embodiments of fertilizer compositions 10 of the instant disclosure, in which the composition includes multiple layers 40 (e.g, a plurality of nitrogen containing material layers interspaced with a plurality of release agent layers),
• Figure 3 A depicts an embodiment of a fertilizer composition 10 having a plurality of coatings/layers 40.
• Figure 3B depicts an embodiment of a fertilizer composition 10 having a combination of thin/thick layers, where one layer (e.g. the thick layer) is discontinuous (e.g. porous, partial covering).
• Figure 3C depicts an embodiment of a fertilizer composition 10 having multiple partial layers 40.
• Figure 3D depicts an embodiment of a fertilizer composition 10 having multiple layers 40, where each layer has varying thicknesses (thick and thin portions),
• urea prills were coated with varices release agent/binder combinations and analysis and testing was performed with the coated fertilizer compositions.
• Commercially available urea prills measuring from -5 to +8 mesh (2.36mm-4mm) were used for coating.
• Raw bauxite residue indicates the "as received" residue, which was dried to remove excess moisture and pulverized to -80 mesh.
• Bauxite residue was sieved according to the mesh ske. The different particle size fractions investigated were: -80 mesh, -80/+200 mesh, and -200 mesh,
• Raw r bauxite residue and HTC were coated with one of three of the following waxes: paraffin (Acros Organics), and two agricultural blends, R-3053 and 7089A (The International Group, Inc.). All pH reduced bauxite residue or sieved residue was coateded with paraffm wax (petroleum).
• All pH reduced bauxite residue or sieved residue was coateded with paraffm wax (petroleum).
• Thirty grams of bauxite residue was used to coat the 150 grams of urea. Half of the bauxite residue was added to the rotating pan before adding the urea prills. The heated prills were then added to the pan and mixed with a spoors to ensure an even coating (as observed via visual inspection).
• the remaining bauxite residue was applied after water was lightly sprayed onto the coated prills. Once the prills appeared to be fully coated (over a 2-5 rain span of time) the remaining bauxite residue was collected (removed) in order to determine the percent coverage,
• the release rate evaluation was based on Tennessee Valley Authority (B!oum et ai, Ag and Food Chem ⁇ 1971, Vol 19, No 5 S 801 -808 (hereinafter 'TV A test”), which provides a published guideline for quantifying the release of urea into a water solution at a specified temperature, over standard periods of time.
• the TVA test provides the following nitrogen release guidelines to be considered a controlled release fertilizer: less than 20% release after 24 hours (1 day); 50% release after 72 hours (three days); and 80% release after 168 hours (one week).
• the nitrogen release rate of each type of coaling was evaluated using a water dissolution test (TVA test), in a mh vial, 7 grams of coated urea product was added to 35mL of deionized water and placed in the oven at 100 °F for 1, 3, and ? days. For each timepoint, the ieachate was collected via gravity filtration. Care was taken to minimize the release of additional urea. The filtrates were analyzed for nitrogen content using HACH High Range Total Nitrogen field test kits.
• TVA test water dissolution test
• FIG. 5-7 Plots providing the nitrogen release as a function of time for the various tests are depicted in Figures 5-7, Referring to these figures, the horizontal bar across each set of data points depicts the target nitrogen release rates based on the guidelines described by the Tennessee Valley Authority test previously described. Error bars represent standard deviation when more than 4 samples were tested. However, when only two samples were measured the maximum and minimum value of the duplicates tested was used to represent error (particle size day 3 S 7 S pH reduced bauxite residue day 3), When duplicates were not available a standard error of 10% was implemented (HTC day 3). None of the coatings tested performed within the target release rates for all checkpoints of the water dissolution test: days 1, 3, and 7.
• a custom bioremediation simulator was initially used to provide a controlled environment for the growth study. Initially poor results suggested that simulator conditions were not optimal for growth, most likely due to lack of air flow and drastic humidity changes.
• Two weeks into the growth study the plants and containers were removed from the simulator and placed indoors, in close proximity to a window to permit light permeating through the windows to reach the containers. Ambient sunlight reached the containers and temperatures neared B5°F at midday with 70 S F conditions in the early morning and evening. The humidity was consistently between 45-50%, Plant health was observed to improve nearly immediately after making this change.
• Each of the containers was filled with soil to within i-2 inches of the maximum capacity in order to account for settling and to maximize soil volume.
• Five onion seeds were planted in each container at a depth of 0.25 inches with 2 inches between seeds. All seeds have approximately 4 inches on each side for growth. Watering was performed using a spray bottle and tap water, as needed, to maintain soil moisture. Two days after planting, nitrogen fertilizer was added near the edges of the container at a depth of 2 Inches to avoid burning the seeds. Container positions were rotated weekly.
• the coated urea fertilizer was evaluated against controls including: urea ⁇ imcoated/immodifsed), UAN (Urea / ammonium nitrate aqueous solution), and ESN (Environmentally Smart Nitrogen, Agrium, Inc.),

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• 2015
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